Scouring cleanser

ABSTRACT

A SCOURING CLEANSER CONTAINING AN ABRASIVE MATERIAL, A HYPOHALIDE-LIBERATING BLEACHING AGENT, AND A WATER SOLUBLE ORGAINC DETERGENT, WHICH HAS IMPROVED STAIN REMOVAL PROPERTIES DUE TO THE INCORPORATION THEREIN OF A COMBINATION OF PHOSPHATE BUILDER SALTS AND AN ALKALI METAL CARBONATE.

United States Patent 3,702,826 SCOURING CLEANSER Mark J. Koceich, Franklin Park, and William Chirash, New Providence, N.J., assignors to Colgate-Palmolive Company, New York, NY. No Drawing. Filed Jan."25, 1971, Ser. No. 109,607 Int. Cl. Clld 7/54 US. Cl. 252-99 4 Claims ABSTRACT OF THE DISCLOSURE A scouring cleanser containing an abrasive material, a hypohalide-liberating bleaching agent, and a water soluble organic detergent, which has improved stain removal properties due to the incorporation therein of a combination of phosphate builder salts and an alkali metal carbonate.

The following invention relates in general to cleansing compositions, and more particularly to powdered scouring cleansers having improved stain removal and cleaning characteristics.

In powdered or granular cleaning compositions for use on solid surfaces, the cleaning action generally depends on three components of the cleanser: an abrasive material, a bleach, and a detergent. The action of the abrasive material must be limited, however, by considerations of damage to the surface being cleaned. That is, an abrading, scrubbing effect that removes particles of dirt and grease is desired, but a cleanser is unsatisfactory if it also removes particles of the surface being cleaned, such as paint or enamel, or causes the surface being cleaned to become scratched.

Thus, the most satisfactory scouring cleansers rely on bleaching and the cleaning actions of detergents to a large extent, and any improvement in the eifectiveness of the bleach or detergent results in a greatly improved cleanser.

The scouring powders used until now, while elfective for many uses, were not entirely satisfactory in the removal of stains, such as tea stains, from surfaces. In order to achieve effective removal of such stains, the stained surface had to be scrubbed and scoured with the cleanser until the surface was damaged. With repeated cleaning, the glaze of tile or porcelain surfaces such as sinks, tables and bathroom fixtures would be removed. This resulted in a dull and unattractive surface, and one that was subsequently more easily stained or dirtied because the glaze was removed.

In accordance with the discovery that is the basis for this invention, an improved scouring cleanser may be formulated, that possesses very effective cleaning and stain removing properties.

Therefore, it is an object of this invention substantially to overcome the disadvantages inherent in use of known scouring cleansers.

It is a further object to provide powdered cleansing compositions having improved cleaning and stain removal characteristics.

Another object is the provision of cleaning compositions specifically and advantageously adapted for use on hard surfaces.

Other objects and advantages will become more apparent hereinafter as the description proceeds.

3,702,826 Patented Nov. 14, 1972 The basis for the present invention is the discovery that a greatly improved scouring cleanser may be prepared by incorporating therein a phosphate builder salt and an alkali metal carbonate.

The combination of the phosphates and carbonates produces a synergistic effect on the cleaning and bleaching ability of a cleansing composition containing certain ingredients as set forth below, the effect being far greater than what would be expected from the use of each material separately in a cleaning composition.

Therefore, the scouring cleansers of the present invention may be broadly defined as those containing: (1) an abrasive material; (2) a hypohalide-liberating bleaching agent; (3) a water soluble organic detergent; and in addition; (4) at least one phosphate builder salt and (5) at least one alkali metal carbonate.

The phosphate builder salts contemplated for use herein include the following: trisodium phosphate, tetrasodium phosphate, sodium acid pyrophosphate, sodium tripolyphosphate, sodium monobasic phosphate, and sodium hexametaphosphate.

The phosphate salt is employed in amounts up to 50% by weight of the composition, amounts from about 1% to about 30% being preferred.

The phosphate salt component of the scouring cleanser may be made up of one of the phosphate salts, or two or more of the phosphate builder salts may be used together.

The alkali metal carbonate for use in the invention is selected from a group of water soluble alkali metal carbonates which are compatible with the other ingredients of the cleanser, and which are in no way detrimental to the desired effects of the composition. Preferred alkali metal carbonates that are especially suitable for use are sodium carbonate, potassium carbonate, monohydrated sodium carbonate, lithium carbonate, and potassium tri hydrated carbonate.

The carbonate may be effectively employed in amounts up to about 50% of the total composition, however, it is preferably used in amounts of about 1% to 30% of the composition.

As with the phosphate, the carbonate component of the cleanser may be made up of one or several of the selected carbonate salts.

The abrasive material, the bleaching agent and the detergent for use in the invention may each be selected from a rather wide range of materials.

For example, the abrasive material may be silica (silicon dioxide), feldspar, pumice, volcanic ash, diatomaceous earth, bentonite, calcium carbonate, talc, etc., or one of the numerous commercially available silicous materials. An especially suitable material is Silex, which is a ground alpha quartz grade of sand, available from the Pennsylvania Pulverizing Company.

The abrasive material is used in an amount of up to about 95% of the composition, most preferably from about 45% to A further component of the cleanser, the bleaching agent, is selected from those compounds capable of liberating hypobromite bromine and/or hypochlorite chlorine in aqueous media. The bleach may be one of a broad class of such agents, so long as it is devoid of free water. Examples of suitable bleaching agents are the dry, particulate heterocyclic N-bromo and N-chloro imides such as trichloro-cyanuric, tribromocyanuric acid, dibromoand dichlorocyanuric acid, and salts thereof with watersolubilizing cations such as potassium and sodium. Such bleaching agents may be employed in admixtures comprising two or more.

Other N-bromo and N-chloro imides may also be used, such as N-brominated and N-chlorinated succinimid, malonimid phthalimide and naphthalimide. Other compounds include the hydantoins, such as 1,3-dibromo and 1,3 dichloro-5,5-dimethylhydantoin; N-monochloro-C,C- dimethylhydantoin methylene-bis (N-bromo-D,C-dimethylhydantoin); 1,3-dibromo and 1,3-dichloro S-isobutylhydantoin; 1,3-bromo and 1,3-dichloro S-methyl-S-ethylhydantoin; 1,3-dibrorno and 1,3-dichloro 5,5-diisobutylhydantoin; 1,3-dibromo and 1,3-dichloro S-methyl-S-namylhydantoin, and the like. Other useful hypohaliteliberating agents comprise tribromomelamine and trichloromelamine. Dry, particulate, water soluble anhydrous inorganic salts are likewise suitable for use such as lithium hypochlorite and hypobromite. The hypohalite-liberating agent may, if desired, be provided in the form of a stable, solid complex or hydrate, such as sodium p-toluene-sulfobromamine-trihydrate, sodium benzene-sulfo-chloraminedihydrate, calcium hypobromite tetrahydrate and calcium hypochlorite tetrahydrate. Brominated and chlorinated trisodium phosphate formed by the reaction of the corresponding sodium hypohalite solution with trisodium phosphate (and water as necessary) likewise comprise efficacious materials.

The present invention contemplates as an additional embodiment the use of bleaching agents capable of liberating hypochlorite as well as hypobromite such as, for example, the N-brominated, N-chlorinated heterocyclic imides, as for example the N-bromo, N-chlorocyanuric acids and salts thereof, e.g., N-monobromo-N, N-dichlorocyanuric acid, N-monobromo-N-monochlorocyanuric acid, N-monobromo-N-monochlorcyanuric acid, sodium- N-monobromo N monochlorocyanurate, potassium-N- monobromo-N-monochlorocyanurate; and the N-brominated, N-chlorinated hydantoin's, e.g., N-bromo-N- chloro-5,5-dimethyl-hydantoin and N-bromo-N-chloro-S- ethyl-S-methyl hydantoin.

The hypohalide-liberating compound is employed in an amount of from 0.1 to 25% by weight of the composition, and preferably in an amount of from about 0.3 to 20% by weight thereof.

The detergent component of the compositions described herein comprises water soluble organic detergent materials which are stable in the presence of the contemplated hypohalite-liberating compounds. These organic detergents may be of the anionic, cationic, amphoteric or non-ionic types provided, of course, that they are compatible with the compositions as a whole and in the proportions employed. In those instances, wherein the detergent is a liquid under normal conditions, as in the case with the non-ionic agents generally, they may be provided in particulate solid form after adsorption upon diatomaceous earth or other similar agents according to procedures well known in the art.

Thus, suitable anionic surface active agents include those surface active or detergent compounds which coritain an organic hydrophobic group and an anionic solubilizing group. Typical examples of anionic solubilizing groups are sulfonate, sulfate, carboxylate, phosphonate and phosphate. Examples of suitable anionic detergents which fall within the scope of the invention include the soaps, such as the water-soluble salts of higher fatty acids, or resin acids, such as may be derived from fats, oils, and waxes of animal, vegetable or marine origin, e.g., the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about 8 to 26, and preferably about 12 to 22, carbon atoms to the molecule.

As examples of suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 15 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium salts of decyl, undecyl, dodecyl, (lauryl), tridecyl, tetradecyl, pentadecyl, or hexadecyl benzene sulfonate and the higher alkyl toluene xylene and phenol sulfonates; alkyl naphthalene sulfonate, ammonium diamyl naphthalene sulfonate, and sodium dinonyl naphthalene sulfonate.

Other anionic detergents are the olefin sulfonates, including long chain alkeno sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents may .be prepared, in known manner, by the reaction of SO with long chain olefius (of 8-25, preferably 12-21 carbon atoms), of the formula RCH-l-CH-R where R is alkyl and R is alkyl or hydrogen, to produce a mixture of.

sultones and alkenesulfonic acids, which mixture is then treated to convert the sultones to sulfonates. Examples of other sulfate or sulfonate detergents are parafiin sulfonates, such as the reaction products of alpha olefins and bisulfites (e.g., sodium bisulfite), e.g., primary paraflin sulfonates of about 10-20, preferably about 15-20, carbon atoms; sulfates of higher alcohols; salts of a-sulfofatty esters (e.g., of about 10 to 20 carbon atoms, such as methly u-sulfomyristate or a-sulfotallowate) Examples of sulfates of higher alcohols are sodium lauryl sulfate, and sodium tallow alcohol sulfate. Turkey Red Oil or other sulfated oils, or sulfates of monoor digly-cerides of fatty acids (e.g., stearic monoglyceride monosulfate), alkyl poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having 1 to 5 ethenoxy groups per molecule); lauryl or higher alkyl glyceryl ether sulfonates; aromatic poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually having 1 to 20 oxyethylene groups per molecule preferably 2-12) may be used.

The suitable anionic detergents include also the acyl sarcosinates (e.g., sodium lauroylsarcosinate) the acyl esters (e.g., oleic acid ester) of isothionates, and the acyl N-methyl taurides (e.g., potassium N-methyl lauroyl-or oleyl tauride).

The most highly preferred water soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, diand triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of the higher alkyl benzene sulfonates, olefin sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates. The particular salt will be suitably selected depending upon the particular formulation and the proportions therein.

Nonionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido or amindo with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.

As examples of nonionic surface active agents which may be used there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about 6 to 30* ethylene oxide units; condensation products of alkyl thiophenols with 10 to 15 ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol monooleate and mannitan monopalmitate, and the condensation products of polypropylene glycol with ethylene oxide.

Cationic surface active agents may also be employed. Such agents are those surface active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.

As examples of suitable synthetic cationic detergents there may be noted the diamines such as those of the type RNHC H NH wherein R is an alkyl group of about 12 to 22 carbon atoms such as N-Z-aminoethyl stearyl amine and N-Z-amino-ethyl myristyl amine; amido-linked amines such as those of the type R CONCH H NH wherein R is an alkyl group of about 9 to 20 carbon atoms, such as N-Z-amino ethyl-stearyl amide and N- amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group which contain 1 to 3 carbon atoms, including such 1 to 3 carbon alkyl groups bearing inert substituents, such as phenyl groups, and there is present an anion such as halogen, acetate, methosulfate, etc. Typical quaternary amonium detergents are ethyl-dimethyl-stearyl amonium chloride, benzyl-dimethylstearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl dilauryl amonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the corresponding methosulfates and acetates.

Examples of specific amphoteric detergents are N- a1kyl-beta-aminoproprionic acid; N-alkyl-beta-imino-dipropionic acid, and N-al kyl, N,N-dimethyl glycine; the al-kyl group may be, for example, that derived from coco fatty alcohol, lauryl alcohol, myristyl alcohol (or a laurylmyristyl mixture), hydrogenated tallow alcohol, cetyl, stearyl, or blends of such alcohols. The substituted aminopropionic and iminodipropionic acids are often supplied in the sodium or other salt forms, which may likewise be used in the practice of this invention. Examples of other amphoteric detergents are the fatty imidazolines such as those made by reacting a long chain fatty acid (e.g., of 10 to 20 carbon atoms) with diethylene triamine and monohalocarboxylic acids having 2 to 6 carbon atoms, e.g., 1-coco-S-hydroxyethyl -carboxymethylimidazoline; betaines containing a sulfonic group instead of the carboxylic group; betaines in which the long chain substituent is joined to the carboxylic group Without an intervening nitrogen atom, e.g., inner salts of Z-trimethylamino fatty acids such as Z-trimethylaminolauric acid, and compounds of any of the previously mentioned types but in which the nitrogen atom is replaced by phosphorous.

The detergent may be added to the other ingredients by spraying. An especially suitable detergent for use in the invention is Detax which is a mixture of alkyl aryl sulfonate detergents prepared by Colgate-Palmolive Company.

The detergent material is employed in concentrations ranging from about 0.5 to about 30 parts by weight of the total composition with a range of about 1 to parts being particularly preferred.

Various other materials may be included in the cleaning compositions of the invention, such as perfumes, coloring agents, etc., so long as these materials do not deleteriously affect the cleaning and stain removal properties of the cleansers.

In a preferred embodiment, a bleach activator is employed, such material being a water soluble compound which acts as a complementary ingredient to the hypohalide-liberating bleaching agent. Inorganic halide salts such as sodium bromide are especially useful as bleaching aids. The sodium bromide acts as an activator for the bleaching agent, and enhances the bleaching effect.

The following examples serve to illustrate the invention but are in no way limiting thereto.

6 EXAMPLE I A scouring cleanser was prepared having the following composition:

This cleansing composition showed improved cleaning and stain removal characteristics when compared with a similar cleaner which was formulated without sodium carbonate.

EXAMPLE .II

The following cleanser compositions were prepared:

Ingredients, percent by weight A Silica Sodium bromide Sodium dodecyl benzene sulfonate (60% active). Trisodiuru phosphate Tripoly phosphate- Sodium carbonate 'lrichlorocyanuric acid 7: Peeps P9 00 Paper 99 m m m s 99 PPP-"PF" 22 It was found that the cleansing ability of samples D and E was greater than samples A and B which contained a phosphate ingredient but did not also contain an alkali carbonate. Similarly, sample C, containing only alkali carbonate as the adjuvant, did not produce as good a cleansing ability as sample D and E.

What is claimed is:

1. In a scouring cleanser composition consisting essentially of (1) an abrasive material,

(2) a hypohalide-liberating bleaching agent, and

(3) a water soluble organic detergent stable in the presence of said hypohalide-liberating bleaching agent, the improvement which comprises incorporating therein 2% of at least one phosphate builder salt, and 2% of at least one water soluble alkali metal carbonate, both based on the total weight of the scouring cleanser.

2. In a scouring cleanser according to claim 1, the improvement which comprises incorporating therein at least one phosphate builder salt that is a member selected from the group consisting of trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium tripolyphosphate, sodium mono-basic phosphate and sodium hexametaphosphate, and at least one water soluble alkali metal carbonate.

3. In a scouring cleanser according to claim 1, the improvement which comprises incorporating therein at least one phosphate builder salt, and at least one alkali metal carbonate which is a member selected from the group consisting of sodium carbonate, potassium carbonate, monohydrated sodium carbonate, lithium carbonate and potassium carbonate trihydrate.

4. An improved scouring cleanser composition according to claim 1 wherein the phosphate builder salt is sodium tripolyphosphate and the alkali metal carbonate is sodium carbonate.

References Cited UNITED STATES PATENTS 3,519,569 7/1970 Diaz 252-99 3,406,116 10/1968 Vitale 252--99 MAYER WEINBLATT, Primary Examiner US. Cl. X.R. 252-187 

